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1 Korean Chem. Eng. Res., Vol. 43, No. 6, December, 2005, pp 종이나섬유를지지체로이용한제올라이트박막의제조 r pn te n 300 ( o 13p r, o 24p }ˆ) Preparation of Zeolite Membranes on Papers or Fibers Kyeong-Keun Song and Kwang Ha Faculty of Applied Chemical Engineering, Chonnam National University, 300, Yongbong-dong, Buk-gu, Gwangju , Korea (Received 13 October 2005; accepted 24 November 2005) k sp, o, o o p vv~ ol p q l l p l rm p p rs m. r, rm p sq n o l rm p NaA( 0.5 µm)m silicalite-1( 0.2 µm) r p m, p r p vv~p l p pn l e. sq rp vv~ ol NaA silicalite-1 rm p p lp, rs p t rq p m, X-ray r m. h Abstract Zeolite membranes on various supports such as filter paper, cotton fiber, and glass fiber filter were prepared by secondary growth hydrothermal synthesis. First, zeolite NaA ( 0.5 µm) and silicalite-1 ( 0.2 µm) crystals were synthesized as zeolite seed crystals, and they were attached to the surfaces of the supports via chemical bonding. Zeolite NaA or silicalite-1 membranes could be synthesized on the supports coated with the seed crystals. The prepared zeolite membranes were observed by scanning electron microscope and analyzed by X-ray diffraction. Key words: Zeolite Membranes, Zeolite NaA, Silicalite-1 1. (zeo) (lite) p p p rm p p } p rp or s v r k mp psp pm r, r p n, ~ ˆ l l p pn p. rm p r, lr, r kr p l, p q p m d l vp q p p p q~(molecular sieve). l rm p l pq p ve pp, p d, ~ kqrp q p p ~, p q p p pp p pn p n [1-5]. lp r tl vp tn k v p. m l, v,, lž, p ˆ m p d p rl qt n ˆl lk To whom correspondence should be addressed. hakwang@chonnam.ac.kr. l v tl p pn vp q, rp. n v p o v l l m r l kr l k kl rn p [1]. rm p p psp v p ~ k~p o q~ jp p. p rp rm p ˆ, p n l r r n l qp k p, v o k ˆ e l n. rm p p } srp p n l vp q pn o rm p p p ˆ p v. p p p pp, p p e p p. r p v v p lr p l, r p r s s v p p v l p [2]. r rm p p p rp l vv~p ol rm p p f. vv~ rvp e, e Ž, o, k Ž, ~ o, k k v p n p [5-19]. p p rs p l [8, 9, 11, 19], p q l [13, 14, 18], 691

2 692 [15] p p. vv~ rm p nkl vv~ ol rm p p eˆ l l rm p p r rp m vv~p v lk, p l vv~ p o p n v lk. vv~l rm p vv~p l l l p rs v, v kp nl vv~ p vp r r } e p [12]., vv~p l r m p jk r p r p pn l r p p nkl rm p p rs p q l p n. l vv~l kp, Ž p l p qeˆ. l e } α-k vv~ ol MFI rm p p r eˆ p l qp (xylene) p v~p e [16, 17]., α-k p FAU rm p p Si/Alp m pm kpml p ˆ, ˆ, v p Œ m ˆ r [18]. p l l r v, vv ~m rm p p lž} l q lp, p p l vp ˆ p lv. rm p p l l rl rn p p q rp v p. q n vv~, kr, ˆ, lr r n p kl l v pv, lp v k, r p rs p o kp p l n kp. p l l rs l d r p spm o o o p vv~ n l l p NaA m silicalite-1p rm p p rs mp, vv~p s l m pql l s m ssz rm p p vv~ sp (Whatman), o o (Whatman), o p n m. vv~ 1cm 1cm r l lˆml 30 k eˆ ml s m, Š ll e 30 k e } m. } vv~ 100 Cl 3e s l p pl o n m oj mš pm om rm p NaAp p rsl p nk ˆ p Ludox HS-40(DuPont, 40 wtí SiO 2 ), sodium silicate(junsei, 98Í Na 2 Si ), sodium aluminate(kanto Chemical, 31-35Í Na 2 O, 34-39Í Al 2, NaAlO 2 ), sodium hydroxide(daejung, 98Í NaOH) p n mp, silicalite-1p p rsl tetraethyl orthosilicate(junsei, 95Í TEOS)m tetrapropylammonium hydroxide (Acros Organics, 10Í TPAOH) n m. k 0.5 µm p rm p NaA Na 2 O:Al 2 :SiO 2 :H 2 O =4:1:2:80p m. dž ƒ l v 20.0 gjp l l NaAlO g p e 10.0 g p p p k 10 k l p nkp o43 o k m. nkp l l NaOH nkp l m l 12e eˆ (Nalgen, 250 ml) l k l m l k l. 100 Cl 6e peˆ m o p, NaA l l p k p v l } 100 Cl 2e k o s m. k 0.2 µmp silicalite-1p TEOS:TPAOH:H 2 O=3:1:330p m. dž ƒl v 58.7 g, TEOS 9.4 g, TPAOH 29.0 gp p nkp v ml k 6e e tl. p k pn l l 180 o C l 6e k p pe. silicalite-1p l l v l } 100 Cl 3e k o s oj mš m oo p rsl vv~l vv~ rm p l p eˆ (p q, primary growth), rm p sq rp vv~l p pn l r r p p sq r ol q (p q, secondary growth)p n m. vv~m rm p rp l (OH) pp, p v eˆ o l Š l n l 3-chloropropyltrimethoxysilane(CPMS) pe l r chloropropyl qn k. n l q polyethylenimine(pei)p n l vv~m sq rp e [20, 21]. NaAp p p p p rs m. v 60 gj l p p dž ƒl Na 2 Si 12.2 g NaAlO gp p e p nkp m. nkp NaOH nkp lt l ml 4e k m. nkp l m, l vv~ v p n p l 100 o C m l k l vv~ ol p m. Silicalite-1 p rs p p. v 58.7 g TPAOH 29.0 gp l l l TEOS 9.4 gp ~ m. nkp ml 6e eˆ k pn l l. l vv~ vp n l 180 o C m l p m. vv~ ol rm p p p k l v l } 100 o C m l k 2e se. rm p NaA silicalite-1 p rs vv~l sq rp r r vp l, p, p m e s p Table 1 2l ˆ l rm p m rm p p r r r p Table 1. Synthesis conditions for preparation of zeolite NaA membranes Method Seeding SiO 2 :Al 2 :Na 2 O:H 2 O Temp. ( o C) Crystallization time (h) A-1 2 : 1 : 3.8 : A-2 2 : 1 : 3.8 : A-3 2 : 1 : 3.8 :

3 Table 2. Synthesis conditions for preparation of silicalite-1 membranes Method Seeding TEOS:TPAOH:H 2 O rl Rigaku(Model R-XAS, Japan) X- r (X-ray diffractometer, XRD) pn m. X- p Ni CuKα- p n mp, 40 kv 40 map s l r (2θ)p 5 ol 60 o v eˆ m. vv~, r m p sq r, rm p p k r ˆ t rq (scanning electron microscope, SEM; Jeol JSM-5400, Japan)p m. 3. y Temp. ( o C) 3-1. pm li oj mš m m rm p NaA p sp ol eˆ o l Table 1 l nk A-1, A-2, A-3 p n mp, vv~ n sp p SEM vp Fig. 1(a)l ˆ l. r lˆm Š lp } sp kl vv~ ol p A-1 pl p ol l v k, p n l rm p NaA r p rm p p rs 693 Crystallization time (h) S-1 3 : 1 : S-2 3 : 1 : S-3 7 : 1 : S-4 7 : 1 : lp, sp l rm p p l pv kk. CPMSm PEI n l NaA sq rp sp l e ˆ vv~(fig. 1(b)) n A-2m A-3 pl l l p NaA sq rm p NaA p q l sp p ˆl p q p SEMp pl (Fig. 1(c)). p e p p pl p p rm p p ˆ k p, p e p A-3 p l rm p p v dp n p l. A-3 pl rm p px- r Ž p Fig. 3(b)l ˆ p, o l sp vv~l p Ž p Fig. 3(a) l ˆ l. l m p r Ž sp ol NaA rm p lpp k p [22]. rm p NaA p rsem v silicalite-1 rsp nl vv~ kl p p(s-1 S-3)l sp ol p v k k. silicalite-1 sq rp l p vv~(fig. 2(a)) n S-2m S-4 pl silicalite-1 p l. S-2 pl p sp r~ mr v mv (Fig. 2(b)), TEOSp kp rp p S-4 p s l sp ol silicalite-1 p r~rp q lp p SEMp pl. S-4 pl p p SEM vp Fig. 2(c)l ˆ p, X- r Ž p Fig. 3(c)l ˆ l. vv~l rm p r pq eˆ o l n CPMSm PEI rm p p l m l Fig. 1. SEM images showing: (a) the morphology of filter paper, (b) zeolite NaA crystals attached to the surface of filter paper, (c) zeolite NaA membrane on filter paper after the reaction A-3. Fig. 2. SEM images showing: (a) silicalite-1 crystals attached to the surface of filter paper, (b) silicalite-1 membrane on filter paper after the reaction S-2, (c) silicalite-1 membrane on filter paper after the reaction S-4. Korean Chem. Eng. Res., Vol. 43, No. 6, December, 2005

4 694 Fig. 5. XRD patterns of (a) cotton, (b) zeolite NaA membrane after the reaction A-2 on cotton. Fig. 3. XRD patterns of (a) a bare filter paper, (b) zeolite NaA membrane on filter paper after the reaction A-3, and (c) silicalite-1 membrane on filter paper after the reaction S-4. s m. sp l v CPMS CPMS/PEI } sq rp pv kp vv~ ol NaA silicalite-1 p v kk li oj mš m o md 94~98Í t p p, k p, Ž, v p p lr p. Mintova p o r, rp } l op p r l rm p o ol m [11, 12]. p l l ol rm p NaA sq rp l p r r ol p e. rm p kl o n } o p A-1 pp o ol NaA p v kkp, rm p pq p ~ o o l l p p pl. l, NaA sq r p CPMS/PEI l q o(fig. 4(a)) n A-2 pl rm p NaA sq p q l p Fig. 4. SEM images showing: (a) zeolite NaA crystals attached to the surfaces of cotton fibers, (b) zeolite NaA membrane on cotton fibers after the reaction A-2. o43 o k op ˆ q lpp p (Fig. 4(b)). Fig. 5l vv~ n om o ol rm p NaA p XRD Ž p ˆ l. o ol silicalite-1 p v kk. rm p s q n v kp S-1 S-3 pl silicalite-1 r p o pl l rp l p p p l, sq n S-2m S-4 pl rm p sq rl p q mv ol lr m p dp pl l l i silicalite-1 m o op t p rm p m p e m k p, l l k p vp l pl rm p p vv ~ p l p [19]. o o m nkl l m nkl NaA p rs llp, o o ol silicalite-1 p rs e m. p nl TEOSm TPAOHp sq rp l p l llr. Silicalite-1 sq rp l pv kp o o n S-1 S-3p e l p v kk. TEOSm TPAOHp l silicalite-1 r p o o l l lpp pl. vv~ n o o m S-1 S-3 pl p o o ol silicalite-1 rp SEM vp Fig. 6(a), (b), (c)l ˆ l. o ol r silicalite-1 sq rp eˆ l vv~ n S-4 pl silicalite-1 r p o o p }n q p q l ppp p (Fig. 6(d)). 4. p l l sp, o, o o p vv~ n l rm p NaA silicalite-1p p rs m. p m p vv~ n nl rm p p vv~

5 rm p p rs 695 Fig. 6. SEM images showing: (a) the glass fibers, (b) silicalite-1 crystals synthesized on the surfaces of glass fibers after the reaction S-1, (c) after the reaction S-3, (d) silicalite-1 membrane on glass filter after the reaction S-4. ol eˆ l ov, p pn l vv~ l r rm p sq r p r t ol rm p p qeˆ nl rm p p q p k pl. p p 2003 r l vol p l l lp, vol. y 1. Bein, T., Synthesis and Applications of Molecular Sieve Layers and Membranes, Chem. Mater., 8(8), (1996). 2. Tavolaro, A. and Drioli, E., Zeolite Membranes, Adv. Mater., 11(12), (1999). 3. Caro, J., Noack, M., Kölsch., P. and Schäfer. R., Zeolite Membranes state of Their Development and Perspective, Microporous Mesoporous Mat., 38(1), 3-24(2000). 4. Noack, M., Kölsch, P., Toussaint, P. and Caro, J., Molecular Sieve Membranes for Industrial Application: Problems, Progress, Solutions, Chem. Eng. Technol., 25(3), (2002). 5. Valtchev, V., Mintova, S. and Konstantinov, L., Influence of Metal Substrate Properties on the Kinetics of Zeolite Film Formation, Zeolites, 15(8), (1995). 6. Valtchev, V., Schoeman, B. J., Hedlund, J., Mintova, S. and Sterte, J., Prepatation and Characterization of Hollow Fibers of Silicalite- 1, Zeolites, 17(5-6), (1996). 7. Valtchev, V., Hedlund, J., Schoeman, B. J., Sterte, J. and Mintova, S., Deposition of Continuous Silicalite-1 Films on Inorganic Fibers, Microporous Materials, 8(1-2), (1997). 8. Okada, K., Shinkawa, H., Takei, T., Hayashi, S. and Yasumori, A., In-situ Coating of Zeolite Na-A on Al 2 -SiO 2 Glass Fibers, J. Porous Mat., 5(2), (1998). 9. Zhang, F.-Z., Fuji, M. and Takahashi, M., In-situ Growth of Continuous b-oriented MFI Zeolite Membranes on Porous α- Alumina Substrates Precoated with a Mesoporous Silica Sublayer, Chem. Mater., 17(5), (2005). 10. Yamazaki, S. and Tsutsumi, K., Synthesis of an A-Type Zeolite Membrane on Silicon Oxide Film-Silicon, Quartz Plate and Quartz Fiber Filter, Microporous Materials, 4(2-3), (1995). 11. Valtchev, V., Mintova, S., Vulchev, I. and Lazarova, V., Influence of Reactive Radicals in Cellulose Fibers on the Formation of Zeolite Coating, J. Chem. Soc., Chem. Commun., (1994). 12. Mintova, S. and Valtchev, V., Deposition of Zeolite A on Vegetal Fibers, Zeolites, 16(1), 31-34(1996). 13. Bernal, M., Xomeritakis, G. and Tsapatsis, M., Tubular MFI Zeolite Membranes Made by Secondary (seeded) Growth, Catal. Today, 67(1-3), (2001). 14. Lai, R. and Gavalas, G. R., Surface Seeding in ZSM-5 Membrane Preparation, Ind. Eng. Chem. Res., 37(11), (1998). 15. Dong, J., Payzant, E. A., Hu, M. Z. C. and Depaoli, D. W., Synthesis of MFI-type Zeolite Membranes on Porous α-alumina Supports by Wet Gel Crystallization in the Vapor Phase, J. Mater. Sci., 38(5), (2003). 16. Lai, Z., Bonilla, G., Diaz, I., Nery, J. G., Sujaoti, K., Amat, M. A., Kokkoli, E., Terasaki, O., Thompson, R. W., Tsapatsis, M. and Vlachos, D. G., Microstructural Optimization of a Zeolite Membrane for Organic Vapor Separation, Science, 300(5618), (2003). 17. Lai, Z., Tsapatsis, M. and Nicolich, J. P., Siliceous ZSM-5 Membranes by Secondary Growth of b-oriented Seed Layers, Adv. Funct. Mater., 14(7), (2004). 18. Hasegawa, Y., Tanaka, T., Watanabe, K., Jeong, B.-H., Kusakabe, K. and Morooka, S., Separation of CO 2 -CH 4 and CO 2 -N 2 Systems Using Ion-exchanged FAU-type Zeolite Membranes with Different Si/Al Ratios, Korean J. Chem. Eng., 19(2), (2002). 19. Larlus, O., Valtchev, V., Patarin, J., Faust, A.-C. and Maquin, B., Preparation of Silicalite-1/Glass Fiber Composites by one- and Two-Step Hydrothermal Synthesis, Microporous Mesoporous Mat., 56(2), (2002). 20. Lee, G. S., Lee, Y.-J., Ha, K. and Yoon, K. B., Preparation of Flexible Zeolite-Tethering Vegetable Fibers, Adv. Mater., 13(19), (2001). 21. Ha, K., Chun, Y. S., Kulak, A., Park, Y. S., Lee, Y.-J. and Yoon, K. B., Polyamines as Strong Covalent Linkers for the Assembly of Mono and Double Layers of Zeolite Crystals on Glass, Stud. Surf. Sci. Catal., 135, (2001). 22. Treacy, M. M. J. and Higgins, J. B., Collection of Simulated XRD Powder Patterns for Zeolites, 4 th Ed., International Zeolite Association, Elsevier(2001). Korean Chem. Eng. Res., Vol. 43, No. 6, December, 2005

국705.fm

국705.fm Carbon Science Vol. 7, No. 1 March 2006 pp. 34-41 Characteristics of Surface Modified Activated Carbons Prepared by Potassium Salt Sequentially After Hydrochloric Acid Treatment Won-Chun Oh, Chong-Sung